Coating solution for charge generation layer and electrophotographic photoreceptor using same

ABSTRACT

Disclosed are a coating solution for forming a charge generation layer, which comprises: 
     (A) a phthalocyanine composition, 
     (B) a binder resin represented by the formula: ##STR1##  wherein R represents an alkylene group, R 1  represents an alkyl group; and m, n and k each represent a ratio of recurring unit numbers and are numerals satisfying the relations of k+m+n=1, n&gt;m&gt;0 and 0.3≧k≧0, 
     (C) at least one of a melamine resin and a benzoguanamine resin in a 1- to 5-fold amount in terms of the weight ratio of the amount of the binder resin, and 
     (D) a solvent having both a hydroxyl group and an ether group in one molecule, 
     and an electrophotographic photoreceptor using the same.

BACKGROUND OF THE INVENTION

This invention relates to a coating solution for forming a charge generation layer and an electrophotographic photoreceptor using the same.

In the prior art, in an electrophotographic photoreceptor in which a photoconductive substance is used as a photosensitive material, inorganic photoconductive substances such as selenium, zinc oxide, titanium oxide and cadmium oxide have been mainly used. However, many of these substances have strong toxicity so that they have also problems in disposal methods.

On the other hand, in general, when organic photoconductive compounds are used, toxicity is weaker and there are advantages in the points of transparency, flexibility, light-weight property, surface smoothness and price as compared with the case of using inorganic photoconductive substances. Therefore, electrophotographic photoreceptors using organic photoconductive compounds have been studied widely. When these photoreceptors are applied to an electrophotographic device according to the Carlson method, an image can be obtained by forming an electrostatic image on the surface of the photoreceptor, developing the photoreceptor by a developer, the so-called toner, charged to the same charge (+ or -) as or a different charge from that of the electrostatic image, and then transferring and fixing a toner image onto a different substrate such as paper.

In recent years, there have been reported many photoreceptors using an organic photoconductive compound and having sensitivity to around 800 nm which is the wavelength of a diode laser region. However, in many of these, a phthalocyanine pigment is used as a charge generation substance, and a photosensitive layer is formed by using a coating solution obtained by dispersing the pigment in a binder resin.

In phthalocyanines which are pigments, not only absorption spectrum and photoconductivity vary depending on central metals, but also these physical properties vary depending on crystal forms. There have been reported several examples of phthalocyanines in which the same central metal is used, but a specific crystal form is selected for an electrophotographic photoreceptor.

For example, there has been reported that various crystal forms exist in titanylphthalocyanines, and charging characteristics, dark decay and sensitivity vary greatly depending on the difference of their crystal forms.

In Japanese Provisional Patent Publication No. 49544/1984, it has been described that a crystal form of titanylphthalocyanine giving strong diffraction peaks at 9.2°, 13.1°, 20.7°, 26.2° and 27.1° of Bragg angles (2θ±0.2°) is preferred, and an X-ray diffraction spectrum chart is shown.

Also, in Japanese Provisional Patent Publication No. 166959/1984, there has been shown a charge generation layer obtained by allowing a vapor deposited film of titanylphthalocyanine to stand in tetrahydrofuran-saturated vapor for 1 to 24 hours to change a crystal form. It has been shown that the X-ray diffraction spectrum shows a smaller number of wide peaks and gives strong diffraction peaks at 7.5°, 12.6°, 13.0°, 25.4°, 26.2° and 28.6° of Bragg angles (2θ).

Further, in Japanese Provisional Patent Publication No. 17066/1989, there has been described that a crystal form of titanylphthalocyanine having main peaks at least at 9.5°, 9.7°, 11.7°, 15.0°, 23.5°, 24.1° and 27.3° of Bragg angles (2θ±0.2°) is preferred.

In Japanese Provisional Patent Publications No. 131243/1990 and No. 214867/1990, there has been described that a crystal form of titanylphthalocyanine having a main diffraction peak at 27.3° of Bragg angles is preferred.

As described above, titanylphthalocyanine exhibits extremely high sensitivity and excellent characteristics by changing a crystal form. However, in a laser printer for which it is used, higher quality and higher precision have been achieved, and an electrophotographic photoreceptor having further high sensitivity characteristic has been demanded.

As a binder resin, there have been used a polyester resin, a polyvinyl chloride resin, a silicone resin, a polystyrene resin, a polyvinyl butyral resin and a phenoxy resin.

In Japanese Provisional Patent Publication No. 183263/1990, there has been shown titanylphthalocyanine with which a polyester resin as a binder resin and 1,2-dichloroethane as a dispersion solvent are used.

In Japanese Provisional Patent Publication No. 231753/1991, there has been shown X type non-metal phthalocyanine with which a modified polyvinyl chloride resin as a binder resin and tetrahydrofuran as a dispersion solvent are used.

In Japanese Provisional Patent Publication No. 10257/1991, there has been shown titanylphthalocyanine with which a polyhydroxystyrene resin as a binder resin and ethanol as a dispersion solvent are used.

In Japanese Provisional Patent Publication No. 33863/1991, there has been shown titanylphthalocyanine with which an acryl resin as a binder resin and cyclohexanone as a dispersion solvent are used.

In Japanese Provisional Patent Publication No. 33863/1991, there has been shown titanylphthalocyanine with which a phenol resin as a binder resin and methyl isobutyl ketone as a dispersion solvent are used.

In Japanese Provisional Patent Publication No. 81861/1992, there has been shown titanylphthalocyanine with which a polyvinyl butyral resin as a binder resin and 1,2-di-methoxyethane as a dispersion solvent are used.

However, in either case, electrophotographic characteristics such as charging characteristics, dark decay and sensitivity are not necessarily satisfactory, and a halogen type solvent having problems in dispersion stability, coating property, electrophotographic characteristics and environmental sanitation is required to be used as a dispersion solvent.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a coating solution for forming a charge generation layer in which the above problems in the prior art can be solved, electrophotographic characteristics such as charging characteristics, dark decay and sensitivity are excellent, and dispersion stability and coating property are good, and an electrophotographic photoreceptor using the same.

The present invention relates to a coating solution for forming a charge generation layer, which comprises:

(A) a phthalocyanine composition,

(B) a binder resin represented by the formula (I): ##STR2## wherein R represents an alkylene group, R¹ represents an alkyl group; and m, n and k each represent a ratio of recurring unit numbers and are numerals satisfying the relations of k+m+n=1, n>m>0 and 0.3≧k≧0,

(C) at least one of a melamine resin and a benzoguanamine resin in an amount of 1- to 5-fold in terms of the weight ratio based on the amount of the binder resin, and

(D) a solvent having both a hydroxyl group and an ether group in one molecule,

and an electrophotographic photoreceptor using the same.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an X-ray diffraction spectrum of a phthalocyanine composition prepared in Preparation example 1.

FIG. 2 is a view illustrating an evaluation method of precipitability of a coating solution for forming a charge generation layer of Example 1, wherein the reference numeral 1 is a stopcock, 2 is a test tube, 3 is a supernatant portion and 4 is a precipitation portion.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the following, the present invention is described in detail.

The phthalocyanine composition (A) of the present invention is not particularly limited, and known phthalocyanine compositions may be used. However, the phthalocyanine composition (A) containing titanylphthalocyanine is preferred from the point of electrophotographic characteristics. Further, the phthalocyanine composition (A) obtained by making amorphous a phthalocyanine mixture of titanylphthalocyanine and a halogenated metal phthalocyanine in which a central metal is trivalent and then treating the resulting amorphous mixture with an organic solvent is preferred from the point of electrophotographic characteristics, and it is more preferred that the above trivalent metal is indium (In). Further, it is preferred from the point of electrophotographic characteristics that the phthalocyanine composition (A) has main diffraction peaks at 7.5°, 22.5°, 24.3°, 25.3° and 28.6° of Bragg angles (2θ±0.2°) in an X-ray diffraction spectrum with Cu Kα.

The titanylphthalocyanine described above can be obtained by referring to, for example, the description of Japanese Provisional Patent Publication No. 71144/1991, and can be prepared, for example, as mentioned below.

To 120 ml of α-chloronaphthalene is added 18.4 g (0.144 mole) of phthalonitrile, and then 4 ml (0.0364 mole) of titanium tetrachloride is added dropwise to the mixture under nitrogen atmosphere. After the dropwise addition, the mixture is heated and reacted at 200° to 220° C. for 3 hours under stirring, and then the reaction mixture is filtered while heating at 100° to 130° C. and the residue is washed with α-chloronaphthalene and then with methanol. The residue is hydrolyzed (90° C., 1 hour) with 140 ml of a deionized water, and this operation is repeated until the solution becomes neutral. The residue is then washed with methanol. Subsequently, the residue was sufficiently washed with N-methylpyrrolidone heated to 100° C. and then washed with methanol. The compound thus obtained is dried by heating at 60° C. under vacuum to obtain titanylphthalocyanine (yield: 46%).

In the above halogenated metal phthalocyanine compounds in which a central metal is trivalent, a trivalent metal as a central metal includes In, Ga and Al, preferably In, and a halogen includes Cl and Br. Said compounds may have a substituent(s) such as a halogen on a phthalocyanine ring. These compounds are known compounds, and among them, for example, a synthetic method of monohalogen metal phthalocyanine and monohalogen metal halogen phthalocyanine is described in Inorganic Chemistry, 19, 3131 (1980) and Japanese Provisional Patent Publication No. 44054/1984.

The monohalogen metal phthalocyanine can be prepared by, for example, the following manner.

To 100 ml of quinoline distilled twice and deoxidized are added 78.2 mmole of phthalonitrile and 15.8 mmole of metal trihalide, and the mixture is refluxed under heating for 0.5 to 3 hours. After gradually cooled, the mixture is cooled to 0° C. and then filtered. The crystal is washed with methanol, toluene and then acetone, and dried at 110° C.

Further, the monohalogen metal halogen phthalocyanine can be prepared by the following manner. After 156 mmole of phthalonitrile and 37.5 mmole of metal trihalide are mixed and melted at 300° C., the mixture is heated for 0.5 to 3 hours to obtain a composition of monohalogen metal halogen phthalocyanine. The composition is washed with α-chloronaphthalene by using a Soxhlet extractor.

In the present invention, as to a composition ratio of the phthalocyanine mixture containing titanylphthalocyanine and a halogenated metal phthalocyanine in which a central metal is trivalent, the content of the titanylphthalocyanine is preferably in the range of 20 to 95% by weight, more preferably in the range of 50 to 90% by weight, particularly preferably in the range of 65 to 90% by weight, most preferably in the range of 75 to 90% by weight from the point of electrophotographic characteristics such as charging characteristics, dark decay and sensitivity.

The phthalocyanine mixture can be made amorphous by the acid pasting method.

For example, 1 g of the phthalocyanine mixture is dissolved in 50 ml of conc. sulfuric acid, and the solution is added dropwise to 1 liter of a deionized water cooled with ice water to be reprecipitated. After filtration, the precipitates are washed with pure water and then with a mixed solution of methanol/pure water until a washing solution has a pH of 2 to 5, and then dried at 60° C. to obtain powder of a phthalocyanine composition. The X-ray diffraction spectrum of the powder thus obtained becomes a spectrum having no clear sharp peak and showing wide amorphous state. As a method of making it amorphous, in addition to the above acid pasting method using conc. sulfuric acid, there is also a method by dry milling.

By treating powder of the phthalocyanine mixture which is thus made amorphous with an organic solvent to change a crystal form, a phthalocyanine composition having main diffraction peaks at 7.5°, 22.5°, 24.3°, 25.3° and 28.6° of Bragg angles (2θ±0.2°) in an X-ray diffraction spectrum with Cu Kα can be obtained.

For example, 1 g of powder of the phthalocyanine mixture which is made amorphous by the above method is added to 10 ml of N-methyl-2-pyrrolidone, toluene or xylene as an organic solvent, and the mixture is heated while stirring (the above powder/organic solvent (in terms of the weight ratio) is 1/1 to 1/100).

The heating temperature is 50° C. to 200° C., preferably 80° C. to 150° C., and the heating time is 1 hour to 10 hours, preferably 1 hour to 8 hours. After completion of the heating while stirring, the mixture is filtered, and the residue is washed with methanol and dried by heating at 60° C. under vacuum to obtain 700 mg of crystal of the phthalocyanine composition of the present invention. As the organic solvent to be used in this treatment, there may be mentioned, for example, alcohols such as methanol, ethanol, isopropanol and butanol, alicyclic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as tetrahydrofuran, dioxane, diethyl ether, ethylene glycol dimethyl ether, 2-methoxyethanol and ethylene glycol diethyl ether, ketones such as 2-ethoxyethyl acetate (Cellosolve acetate, trade name), acetone, methyl ethyl ketone, cyclohexanone, isophorone and 1,3-dimethyl-2-imidazolidinone, esters such as methyl acetate and ethyl acetate, non-chlorine type organic solvents such as dimethyl sulfoxide, dimethylformamide, phenol, cresol, anisole, nitrobenzene, acetophenone, benzyl alcohol, pyridine, N-methyl-2-pyrrolidone, quinoline, tetralin and picoline, and chlorine type organic solvents such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, carbon tetrachloride, chloroform, chloromethyloxirane, chlorobenzene and dichlorobenzene.

Among these, ketones and non-chlorine type organic solvents are preferred, and among them, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, pyridine, methyl ethyl ketone and diethyl ketone are preferred.

The electrophotographic photoreceptor of the present invention has a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance, provided on a conductive substrate.

The coating solution for forming a charge generation layer of the present invention contains the phthalocyanine composition (A), the binder resin (B) represented by the formula (I), at least one of the melamine resin and benzoguanamine resin (C) in a 1- to 5-fold amount (weight ratio) of the amount of the binder resin (B) and the solvent (D) having both a hydroxyl group and an ether group in one molecule, as essential components.

The binder resin (B) represented by the formula (I) is a resin which has been already known, and as a commercially available product, there may be mentioned, for example, a polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) and polyvinyl butyral resins Ethlec BMS (trade name, produced by Sekisui Kagaku Kogyo Co.) and Denka Butyral #5000-A (trade name, produced by Denki Kagaku Kogyo Co.).

In the formula (I), R is an alkylene group preferably having 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, more specifically, there may be mentioned a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, etc. R¹ is a straight or branched alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, more specifically, there may be mentioned a methyl group, an ethyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, a dodecyl group, an undecyl group, etc.

In the formula (I), in the case of k>0.3, dispersibility of the coating solution for forming a charge generation layer is worsened, and in the case of m≧n, humidity resistance of the electrophotographic photoreceptor and dispersibility of the coating solution for forming a charge generation layer are worsened. The polymerization degree of the binder resin (B) represented by the formula (I) is preferably in the range of 300 to 3,000. If it is less than 300, mechanical strength of the photoconductive layer tends to be poor and also tends to be corroded by a coating solvent of a charge transport layer which is coated for preparing a composite type electrophotographic photoreceptor, while if it exceeds 3,000, operatability or working property during preparation of the photoconductive layer tends to be worsened.

The coating solution for forming a charge generation layer of the present invention contains at least one of the melamine resin and benzoguanamine resin (C) as an essential component(s). As the melamine resin or benzoguanamine resin, there have been generally known those obtained by treating an amino group bonded to a triazine ring with formaldehyde to be converted into methylol and modifying methylol with an alcohol. The melamine resin is commercially available, for example, as Melan 289 (trade name, produced by Hitachi Chemical Co., Ltd.) and the benzoguanamine resin is commercially available, for example, as Melan 331 (trade name, produced by Hitachi Chemical Co., Ltd.). The melamine resin or benzoguanamine resin forms a photoconductive layer having excellent film formation property, dispersibility, adhesion property and humidity resistance and has effects of improving sensitivity, responsibility to light, potential-maintaining property, residual potential and image characteristics. It is particularly preferred that 50% or more of amino groups bonded to triazine rings are converted into methylols and 50% or more of said methylols are modified. As an alcohol to be used for modification, propyl alcohol, n-butanol and isobutanol are preferred.

The melamine resin and benzoguanamine resin (C) are used in total in a 1- to 5-fold amount (weight ratio) of the amount of the binder resin (B) represented by the formula (I) . The amount to be used is preferably a 1.01- to 5-fold amount, more preferably a 1.3- to 3-fold amount, particularly preferably a 1.5- to 2.5-fold amount. If the amount to be used is too small, water absorption is increased, whereby bad influences such as blurring of an image and lowering of potential-maintaining property and sensitivity are brought about when said resin is used for an electrophotograph. On the other hand, if the amount to be used is too large, water absorption is increased, whereby film properties of a charge generation layer become hard and fragile to lower mechanical characteristics.

As the solvent (D) having both a hydroxyl group and an ether group in one molecule of the present invention, there may be mentioned, for example, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 2-hexyloxyethanol, tetrahydrofurfuryl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and 1-propoxy-2-propanol. Among them, 1-methoxy-2-propanol is preferred from the points of dispersibility, dispersion stability (e.g. the phthalocyanine composition (A) is hardly precipitated), coating property and environmental sanitation.

A solvent (E) other than the above solvent (D) having both a hydroxyl group and an ether group in one molecule may be used, but it is preferred that the solvent (D) having both a hydroxyl group and an ether group in one molecule is contained in the range of 20 to 100% by weight based on the total amount of the solvents. If the amount of the solvent (D) is less than 20% by weight, film quality of the photoconductive layer is easily worsened, whereby bad influences are easily exerted on almost all electrophotographic characteristics such as sensitivity, potential-maintaining property, residual potential and image quality.

Further, when the evaporation rate of the solvent (E) other than the solvent (D) having both a hydroxyl group and an ether group in one molecule is defined as v2 and that of the solvent (D) having both a hydroxyl group and an ether group in one molecule is defined as v1, it is preferred to select the solvent (D) and the solvent (E) so as to have a relationship of v1<v2. Here, the evaporation rate is a value measured at 25° C. under a pressure of 1013 hectopascal (760 mmHg). In the case of v1≧v2, it may be difficult to obtain a desired film thickness, a phenomenon of poor uniformity of a film thickness may be observed or unevenness of image density may be caused.

In the coating solution for forming a charge generation layer, it is preferred that the phthalocyanine composition (A) and, if necessary, an organic pigment generating a charge to be used are contained, and that the total amount of the binder resin (B) and the melamine resin and/or benzoguanamine resin (C) is controlled to an amount in the range of 5 to 500% by weight, more preferably 20 to 300% by weight, based on the total amount of the phthalocyanine composition (A) and the above organic pigment (charge generation substance). The coating solution for forming a charge transport layer contains a charge transport substance, and the amount of a binder for a charge transport layer is preferably controlled to an amount of 500% by weight or less based on the amount of the charge transport substance. If the charge transport substance is a compound having a low molecular weight, a binder is preferably contained in an amount of 50% by weight or more based on the amount of the charge transport substance.

As the organic pigment generating a charge mentioned above, there may be mentioned, for example, an azo pigment and a squaraine pigment.

As the above charge transport substance, there may be mentioned a compound having a high molecular weight such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinyl pyrene, polyvinyl indoloquinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, polyvinyl acridine and polyvinyl pyrazoline, and the compound having a low molecular weight such as fluorenone, fluorene, 2,7-dinitro-9-fluorenone, 4H-indeno(1,2,6)thiophen-4-one, 3,7-dinitrodibenzothiophene-5-oxide, 1-bromopyrene, 2-phenylpyrene, carbazole, N-ethylcarbazole, 3-phenylcarbazole, 3-(N-methyl-N-phenylhydrazone)methyl-9-ethylcarbazole, 2-phenylindole, 2-phenylnaphthalene, oxadiazole, 2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole, 1-phenyl-3-(4-diethylaminostyryl)-5-(4-diethylaminostyryl)-5-(4-diethylaminophenyl)pyrazoline, 1-phenyl-3-(p-diethylaminophenyl)pyrazoline, p-(dimethylamino)-stilbene, 2-(4-dipropylaminophenyl)-4-(4-dimethylaminophenyl)-5-(2-chlorophenyl)-1,3-oxazole, 2-(4-dimethylaminophenyl)-4-(4-dimethylaminophenyl)-5-(2-fluorophenyl)-1,3-oxazole, 2-(4-diethylaminophenyl)-4-(4-dimethylaminophenyl)-5-(2-fluorophenyl)-1,3-oxazole, 2-(4-dipropylaminophenyl)-4-(4-dimethylaminophenyl)-5-(2-fluorophenyl)-1,3-oxazole, imidazole, chrysene, tetraphene, acridene, triphenylamine, benzidine and derivatives thereof. As the charge transport substance, the benzidine derivative represented by the following formula (II) is particularly preferred. ##STR3## wherein R¹ and R² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, two R³ s each independently represents a hydrogen atom or an alkyl group, Ar¹ and Ar² each independently represents an aryl group, and p, q, r and s each represent an integer of 1 to 5.

In the formula (II), the alkyl group may include those having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and a tert-butyl group. The alkoxy group may include those having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group and an iso-propoxy group. The aryl group may include a phenyl group, a tolyl group, a biphenyl group, a terphenyl group and a naphthyl group. The fluoroalkyl group may include those having 1 to 3 carbon atoms such as a trifluoromethyl group, a trifluoroethyl group and a heptafluoropropyl group. The fluoroalkoxy group may include those having 1 to 4 carbon atoms such as a trifluoromethoxy group, a 2,3-difluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 1H,1H-pentafluoropropoxy group, a hexafluoro-isopropoxy group, a 1H,1H-pentafluorobutoxy group, a 2,2,3,4,4,4-hexafluorobutoxy group and a 4,4,4-trifluorobutoxy group. Specific examples of the compound represented by the formula (II) may include Compounds No. 1 to No. 6 shown below. ##STR4##

As the binder for a charge transport layer which can be used in the above charge transport layer, there may be mentioned a silicone resin, a polyamide resin, a polyurethane resin, a polyester resin, an epoxy resin, a polyketone resin, a polycarbonate resin, a polyacrylic resin, a polystyrene resin, a styrene-butadiene copolymer, a poly(methyl methacrylate) resin, a polyvinyl chloride, an ethylene-vinyl acetate copolymer, a vinyl chloride-vinyl acetate copolymer, a polyacrylamide resin, a polyvinylcarbazole, a polyvinyl pyrazoline and a polyvinyl pyrene. Further, a thermosetting resin and a photocuring resin which are crosslinked by heat and/or light may be also used. In either case, the binder is not particularly limited so long as it is a resin which has insulation property and can form a film under normal conditions, and a resin which is cured by heat and/or light to form a film.

To the coating solution for forming a charge generation layer and the coating solution for forming a charge transport layer, additives such as a plasticizer, a flowability imparting agent and a pinhole preventing agent may be added, if necessary. The plasticizer may-include paraffin halide, dimethylnaphthalene and dibutylphthalate, the flowability imparting agent may include Modaflow (trade name, produced by Monsant Chemical Co.) and Akulonal 4F (trade name, produced by BASF Co.), and the pinhole preventing agent may include benzoin and dimethylphthalate. These may be suitably selected and used, and the amounts thereof may be suitably determined.

The electrophotographic photoreceptor of the present invention can be obtained by providing, if necessary, a subbing layer by coating a coating solution for a subbing layer on a conductive substrate such as a paper or a plastic film subjected to conductive treatment, a plastic film on which a metal foil such as aluminum is laminated and a metal plate and then drying the coating solution, providing a charge generation layer thereon by coating the coating solution for forming a charge generation layer of the present invention and then drying the coating solution, and then providing a charge transport layer thereon by coating a coating solution for forming a charge transport layer and then drying the coating solution.

The charge generation layer preferably has a thickness of 0.001 to 10 μm, particularly preferably 0.2 to 5 μm. If it is less than 0.001 μm, it is difficult to form the charge generation layer uniformly, while if it exceeds 10 μm, electrophotographic characteristics tend to be lowered. The thickness of the charge transport layer is preferably 5 to 50 μm, particularly preferably 8 to 25 μm. If the thickness is less than 5 μm, initial potential is lowered, while if it exceeds 50 μm, sensitivity tends to be lowered.

As a coating method, there may be employed a spin coating method, a dip coating method, a roll coating method, an applicator coating method and a wire bar coating method.

When the phthalocyanine composition of the present invention is coated by the spin coating method, it is preferred that spin coating is carried out at a rotation number of 200 to 4,000 rpm by using a coating solution for forming a charge generation layer obtained by dissolving or dispersing the phthalocyanine composition (A), the binder resin (B) represented by the formula (I) and the melamine resin or benzoguanamine resin (C) uniformly in the solvent (D) having both a hydroxyl group and an ether group in one molecule. The coating solution for forming a charge generation layer may be coated by a coating method other than the spin coating method, such as a dip coating method, a roll coating method, an applicator coating method and a wire bar coating method, followed by drying, to form a charge generation layer.

The electrophotographic photoreceptor of the present invention may have a protective layer on the surface thereof.

EXAMPLES

The present invention is described in detail by referring to Examples.

Preparation example 1

In 50 ml of sulfuric acid was dissolved 1 g of a phthalocyanine mixture comprising 0.75 g of titanylphthalocyanine and 0.25 g of chloroindium phthalocyanine, and the solution was stirred at room temperature for 30 minutes. Subsequently, the solution was added dropwise to one liter of a deionized water cooled with ice water over about 40 minutes to be precipitated. The mixture was further stirred for 1 hour under cooling and left to stand for one day. After the supernatant was removed by decantation, the precipitates were obtained by centrifugation. These precipitates were washed with a deionized water six times. The pH and conductivity of the washing water after it was washed six times were measured. The pH was measured by using Model pH51 (trade name, manufactured by Yokogawa Denki Co.). Further, the conductivity was measured by Model SC-17A (trade name, manufactured by Shibata Kagaku Kikai Kogyo Co.). The pH of the washing water was 3.3, and the conductivity was 65.1 μS/cm. Subsequently, the precipitates were washed with methanol three times and then dried under vacuum by heating at 60° C. for 4 hours.

Next, 1 g of the resulting product was added to 10 ml of 1,3-dimethyl-2-imidazolidinone, and the mixture was heated and stirred (150° C., one hour). After filtration, the residue was washed with methanol and dried under vacuum by heating at 60° C. for 4 hours to obtain crystal of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of this crystal is shown in FIG. 1.

Preparation example 2

Crystal of the phthalocyanine composition was obtained according to Preparation example 1 except for using bromoindium phthalocyanine in place of chloroindium phthalocyanine, using toluene in place of 1,3-dimethyl-2-imidazolidinone and carrying out heating and stirring at 110° C. for one hour.

Preparation example 3

Crystal of the phthalocyanine composition was obtained according to Preparation example 1 except for using chlorogallium phthalocyanine in place of chloroindium phthalocyanine, using xylene in place of 1,3-dimethyl-2-imidazolidinone and carrying out heating and stirring at 120° C. for 3 hours.

Preparation example 4

Crystal of the phthalocyanine composition was obtained according to Preparation example 1 except for using chloroaluminum phthalocyanine in place of chloroindium phthalocyanine, using tetralin in place of 1,3-dimethyl-2-imidazolidinone and carrying out heating and stirring at 150° C. for 3 hours.

Preparation example 5

Crystal of the phthalocyanine composition was obtained according to Preparation example 1 except for using bromoindium phthalocyanine in place of chloroindium phthalocyanine, using dioxane in place of 1,3-dimethyl-2-imidazolidinone and carrying out heating and stirring at 110° C. for 8 hours.

Preparation example 6

In 50 ml of sulfuric acid was dissolved 1 g of copper phthalocyanine (produced by Kodak Co.), and the mixture was stirred at room temperature for 30 minutes. Subsequently, the solution was added dropwise to one liter of a deionized water cooled with ice water over about 40 minutes to be precipitated. The mixture was further stirred for one hour under cooling and left to stand for one day. After the supernatant was removed by decantation, the precipitates were obtained by centrifugation. These precipitates were washed with a deionized water six times. The pH and conductivity of the washing water after it was washed six times were measured. The pH was measured by using Model pH51 (trade name, manufactured by Yokogawa Denki Co.). Further, the conductivity was measured by Model SC-17A (trade name, manufactured by Shibata Kagaku Kikai Kogyo Co.). The pH of the washing water was 3.9, and the conductivity was 82.6 μ/cm. Subsequently, the precipitates were washed with methanol three times and then dried under vacuum by heating at 60° C. for 4 hours.

Next, 1 g of the resulting product was added to 10 ml of orthoxylene, and the mixture was heated and stirred (130° C., 3 hours). After filtration, the residue was washed with methanol and dried under vacuum by heating at 60° C. for 4 hours to obtain crystal of β type copper phthalocyanine.

Preparation example 7

Crystal of the phthalocyanine composition was prepared according to Preparation example 1 except for changing the heating time in 1,3-dimethyl-2-imidazolidinone to 12 hours.

Preparation example 8

Crystal of the phthalocyanine composition was obtained according to Preparation example 7 except for using bromoindium phthalocyanine in place of chloroindium phthalocyanine, using toluene in place of 1,3-dimethyl-2-imidazolidinone and carrying out heating and stirring at 110° C. for 12 hours.

Preparation example 9

Crystal of the phthalocyanine composition was obtained according to Preparation example 7 except for using chlorogallium phthalocyanine in place of chloroindium phthalocyanine, using xylene in place of 1,3-dimethyl-2-imidazolidinone and carrying out heating and stirring at 120° C. for 12 hours.

Preparation example 10

Crystal of the phthalocyanine composition was obtained according to Preparation example 7 except for using chloroaluminum phthalocyanine in place of chloroindium phthalocyanine, using tetralin in place of 1,3-dimethyl-2-imidazolidinone and carrying out heating and stirring at 150° C. for 24 hours.

EXAMPLE 1

10 g of the phthalocyanine composition prepared in Preparation example 1 as the phthalocyanine composition (A) which was a charge generation substance, 3.06 g of a polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.)(the compound of the formula (I) wherein R is methylene group, R¹ is methyl group, k is 0.03, m is 0.27 and n is 0.70) as the binder resin (B), 13.61 g of a melamine resin ML289 (trade name, produced by Hitachi Chemical Co., Ltd., solid content: 51.0% by weight) as the melamine resin or benzoguanamine resin (C) and 380 g of 2-ethoxyethanol as the solvent (D) having both a hydroxyl group and an ethyl group in one molecule were mixed, and the mixture was dispersed by a ball mill.

The coating solution for forming a charge generation layer thus obtained was charged into a test tube with a stopcock, having a inner diameter of 15 mm and a length of 20 cm. The test tube was tightly closed with the stopcock and left to stand at 23° C. for 60 days. When precipitability was measured, it was 2.3% (see FIG. 2). The precipitability was represented by b/a×100 (%) wherein a is a height of the whole coating solution in the test tube and b is a width of the supernatant portion in the test tube.

When water absorption was measured from weight change during drying of the coating solution for forming a charge generation layer and under moisture conditioning with an NH₄ H₂ PO₄ -saturated aqueous solution, it was 0.7%. The water absorption was measured by charging the coating solution for forming a charge generation layer into a laboratory dish so as to have a dried thickness of 8 μm, drying the solution at 120° C. for one hour, leaving the laboratory dish to stand at 23° C. for 72 hours in a desiccator in which silica gel was placed, then measuring a weight of W₁, leaving the laboratory dish to stand for 72 hours in a vessel (relative humidity: 93%, 23° C.) into which an NH₄ H₂ PO4-saturated aqueous solution was charged and then measuring a weight of W₂, and represented by (W₂ -W₁)/W₁ ×100 (%).

The coating solution for forming a charge generation layer obtained was coated on a conductive substrate (an aluminum plate of 100 mm×100 mm×0.1 mm) by the dip coating method and dried at 120° C. for 1 hour to obtain a charge generation layer having a thickness of 0.5 μm.

A coating solution for forming a charge transport layer, obtained by mixing 15 g of the above charge transport substance No. 4, 15 g of a polycarbonate resin Upilon S-3000 (trade name, produced by Mitsubishi Gas Kagaku Co.) and 155 g of methylene chloride was coated on the substrate of the above charge generation layer by the dip coating method, and dried at 120° C. for 1 hour to form a charge transport layer having a thickness of 20 μm, whereby an electrophotographic photoreceptor was obtained.

The electrophotographic characteristics of this electrophotographic photoreceptor were measured by an electrophotographic characteristics-evaluating device Cynthia 30 (trade name, GENTEC Co. at Tokyo, Japan). The photoreceptor was charged by corona discharging of -5 kV under dark condition, and initial charge V₀ (-V) after 10 seconds was evaluated. Corona voltage was controlled so that initial charge potential was 700 V, and measured were dark dacay DDR (%) after 5 seconds, sensitivity E_(1/2) (mJ/m²) when exposed to light having a wavelength of 780 nm with a light volume of 20 mW/m², and residual potential Vr (-V) 1 second after initiation of exposure.

The dark decay was defined according to the following expression: ##EQU1## As a result, V₀ =850 (-V), DDR=90.2 (%), E_(1/2) =4.10 (mJ/m²) and Vr=47 (-V).

Separately, the electrophotographic photoreceptor was pasted to an aluminum drum, and the drum was set in a laser beam printer in which charging, exposure, development, transfer and cleaning were carried out. When image quality was evaluated (charge: -400 V, exposure: 780 nm, 20 mJ/m², erase: 560 nm), it was A. The standard for evaluating image quality is shown below.

(Evaluation)

A: Image having high quality without defects.

B: A few fogs were observed.

B': A large number of fogs were observed.

C: A few black spots were observed.

C': A large number of black spots were observed.

D: A few white spots were observed.

D': A large number of white spots were observed.

E: Image density was low.

F: Whole printed matter was black or image was not obtained at all (whole printed matter was white).

EXAMPLES 2 TO 15

Electrophotographic photoreceptors were prepared and evaluated according to Example 1 except for using the titanylphthalocyanine compositions obtained in Preparation examples 2 to 5. The results are shown in Table 1 together with the results of Example 1.

                                      TABLE 1     __________________________________________________________________________                         Initial                              Dark        Residual            Charge Charge                         charge                              decay                                   Sensitivity                                          potential     Water            generation                   transport                         V.sub.0                              DDR  E.sub.1/2                                          Vr    Precipitability                                                        absorption                                                               Image            substance                   substance                         (-V) (%)  (mJ/m.sup.2)                                          (-V)  (%)     (%)    quality     __________________________________________________________________________     Example 1            Preparation                   No. 1 850  90.2 4.10   47    2.3     0.7    A            example 1     Example 2            Preparation                   No. 1 900  88.3 3.82   35    2.1     0.9    A            example 2     Example 3            Preparation                   No. 1 880  85.6 3.35   63    1.8     1.7    B            example 3     Example 4            Preparation                   No. 1 920  88.8 3.61   58    3.5     1.4    A            example 4     Example 5            Preparation                   No. 1 930  90.8 3.24   31    2.0     0.6    A            example 5     Example 6            Preparation                   No. 4 870  90.4 2.77   70    3.7     1.8    A            example 1     Example 7            Preparation                   No. 4 760  86.5 3.89   55    2.6     0.9    A            example 2     Example 8            Preparation                   No. 4 810  82.2 4.02   43    4.1     0.7    A            example 3     Example 9            Preparation                   No. 4 750  90.3 3.78   61    4.8     1.4    A            example 4     Example 10            Preparation                   No. 4 890  91.2 2.75   40    1.7     0.6    A            example 5     Example 11            Preparation                   No. 3 940  91.1 2.94   47    4.7     1.8    A            example 1     Example 12            Preparation                   No. 3 850  89.9 3.55   58    4.6     0.9    A            example 2     Example 13            Preparation                   No. 3 830  90.2 3.48   36    2.9     1.5    A            example 3     Example 14            Preparation                   No. 3 910  90.5 3.50   46    2.8     1.6    A            example 4     Example 15            Preparation                   No. 3 950  92.1 2.89   34    1.8     0.8    A            example 5     __________________________________________________________________________

EXAMPLES 16 TO 27

Electrophotographic photoreceptors were prepared and evaluated according to Example 1 except for using the titanylphthalocyanine compositions obtained in Preparation examples 7 to 10. The results are shown in Table 2.

                                      TABLE 2     __________________________________________________________________________                         Initial                              Dark        Residual            Charge Charge                         charge                              decay                                   Sensitivity                                          potential     Water            generation                   transport                         V.sub.0                              DDR  E.sub.1/2                                          Vr    Precipitability                                                        absorption                                                               Image            substance                   substance                         (-V) (%)  (mJ/m.sup.2)                                          (-V)  (%)     (%)    quality     __________________________________________________________________________     Example 16            Preparation                   No. 1 390  50.2 9.8    81    1.8     0.8    B            example 7     Example 17            Preparation                   No. 1 360  46.2 7.9    35    2.6     1.0    B            example 8     Example 18            Preparation                   No. 1 240  65.0 8.4    55    3.7     1.9    A            example 9     Example 19            Preparation                   No. 1 330  55.2 11.5   11    5.8     2.0     B'            example 10     Example 20            Preparation                   No. 4 280  35.3 7.3    46    2.9     1.8    B            example 7     Example 21            Preparation                   No. 4 150  41.2 8.8    25    2.5     1.9    B            example 8     Example 22            Preparation                   No. 4 330  22.3 2.9    18    1.3     1.0    B            example 9     Example 23            Preparation                   No. 4 250  27.8 7.8    3     3.6     1.2    B            example 10     Example 24            Preparation                   No. 3 271  56.8 14.3   22    3.8     1.8    C            example 7     Example 25            Preparation                   No. 3 180  60.2 8.5    74    6.6     0.9    B            example 8     Example 26            Preparation                   No. 3 190  56.6 10.2   30    5.1     1.7    B            example 9     Example 27            Preparation                   No. 3 350  33.9 8.4    14    1.9     1.5    B            example 10     __________________________________________________________________________

EXAMPLES 28 TO 34

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 to 7 except for using a polyvinyl butyral resin Ethlec BMS (trade name, produced by Sekisui Kagaku Kogyo Co.)(the compound of the formula (I) wherein R is an n-butylene group, R¹ is a methyl group, k is 0.05, m is 0.25 and n is 0.70) in place of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) as the binder resin (B) and formulating 2.22 g of the polyvinyl butyral resin Ethlec BMS (trade name, produced by Sekisui Kagaku Kogyo Co.) and 15.25 g of the melamine resin ML289 (trade name, produced by Hitachi Chemical Co., Ltd.). The results are shown in Table 3.

                                      TABLE 3     __________________________________________________________________________                            Initial                                 Dark       Residual            Charge                  Charge                        Binder                            charge                                 decay                                     Sensitivity                                            potential    Water            generation                  transport                        resin                            V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image            substance                  substance                        (B) (-V) (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Example 28            Preparation                  No. 1 Ethlec                            910  90.2                                     3.8    41   1.5     2.1   A            example 1   BMS     Example 29            Preparation                  No. 1     930  86.5                                     2.9    55   2.6     2.8   B            example 2     Example 30            Preparation                  No. 1     1140 85.0                                     4.4    35   2.7     2.6   A            example 3     Example 31            Preparation                  No. 1     840  94.6                                     3.5    48   3.8     2.7   A            example 4     Example 32            Preparation                  No. 1     1160 95.0                                     2.7    32   1.4     1.6   A            example 5     Example 33            Preparation                  No. 4     910  85.3                                     2.9    50   4.0     2.9   A            example 1     Example 34            Preparation                  No. 4     880  91.4                                     3.8    40   3.2     1.8   A            example 2     __________________________________________________________________________

EXAMPLES 35 TO 40

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 to 3 except for using components (C) shown in Table 4 in place of the melamine resin ML289 (trade name, produced by Hitachi Chemical Co., Ltd.) as the component (C) and formulating 3.95 g of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) and 12.1 g of the components (C). The results are shown in Table 4. In Table 4, ML245 is a melamine resin ML245 (trade name, produced by Hitachi Chemical Co., Ltd., solid content: 50.0% by weight) and ML365 is a benzoguanamine resin ML365 (trade name, produced by Hitachi Chemical Co., Ltd., solid content: 50.0% by weight). Further, water absorption was evaluated from weight change during drying with silica gel and under moisture conditioning with an NH₄ H₂ PO₄ -saturated aqueous solution, and the results are also shown in Table 4.

                                      TABLE 4     __________________________________________________________________________                            Initial                                 Dark       Residual                 Charge                       Charge                            charge                                 decay                                     Sensitivity                                            potential    Water     Component   generation                       transport                            V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image     (C)         substance                       substance                            (-V) (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Example 35           ML245 Preparation                       No. 1                            940  86.5                                     3.8    61   1.5     1.3   A                 example 1     Example 36           ML365 Preparation                       No. 1                            870  90.2                                     2.9    35   2.3     0.6   A                 example 1     Example 37           ML245 Preparation                       No. 1                            940  85.0                                     4.4    43   2.1     0.7   A                 example 2     Example 38           ML365 Preparation                       No. 1                            860  94.6                                     3.5    27   2.2     0.3   A                 example 2     Example 39           ML245 Preparation                       No. 1                            850  85.3                                     2.9    58   2.4     0.8   A                 example 3     Example 40           ML365 Preparation                       No. 1                            950  91.4                                     3.8    42   1.8     0.5   A                 example 3     __________________________________________________________________________

Comparative Examples 1 to 3

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 to 3 except for using an acryl resin Almatex WP640 (trade name, produced by Mitsui Toatsu Kagaku Co.) in place of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) as the binder resin (B). The results are shown in Table 5.

                                      TABLE 5     __________________________________________________________________________                            Initial                                 Dark       Residual            Charge                  Charge                       Binder                            charge                                 decay                                     Sensitivity                                            potential    Water            generation                  transport                       resin                            V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image            substance                  substance                       (B)  (-V) (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Comparative            Preparation                  No. 1                       Almatex                            440  32.3                                     13.8   11   25.3    2.1   F     example 1            example 1  WP640     Comparative            Preparation                  No. 1     370  14.2                                     11.5   6    42.8    1.3   F     example 2            example 2     Comparative            Preparation                  No. 1     540  34.1                                     7.8    75   51.1    1.8    C'     example 3            example 3     __________________________________________________________________________

Comparative Examples 4 to 6

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 to 3 except for using an epoxy resin Epikote 828 (trade name, produced by Yuka Shell Epoxy Co.) in place of the melamine resin ML289 (trade name, produced by Hitachi Chemical Co., Ltd.) as the component (C) and formulating 3.0 g of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) and 7.0 g of the epoxy resin Epikote 828 (trade name, produced by Yuka Shell Epoxy Co.). The results are shown in Table 6.

                                      TABLE 6     __________________________________________________________________________                            Initial                                 Dark       Residual                 Charge                       Charge                            charge                                 decay                                     Sensitivity                                            potential    Water            Epoxy                 generation                       transport                            V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image            resin                 substance                       substance                            (-V) (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Comparative            Epikote                 Preparation                       No. 1                            340  46.2                                     1.8    8    54.4    4.7   F     example 4            828  example 1     Comparative Preparation                       No. 1                            470  43.3                                     1.9    11   43.3    4.3   F     example 5   example 2     Comparative Preparation                       No. 1                            180  21.0                                     0.4    2    48.4    5.6   F     example 6   example 3     __________________________________________________________________________

EXAMPLES 41 TO 46

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 and 2 except for changing the formulation amounts of the binder resin (B) and the melamine resin or benzoguanamine resin (C) so that the weights (unit: g) of the binder resins (B) and the weights (unit: g, solid content) of the melamine resin or benzoguanamine resin (C) had relations as shown in Table 7. The results are shown in Table 7.

                                      TABLE 7     __________________________________________________________________________                 Binder     Initial                                 Dark       Residual     Charge      resin                      Component                            charge                                 decay                                     Sensitivity                                            potential    Water     generation  (B)  (C)   V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image     substance   (g)  (g)   (-V) (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Example 41           Preparation                 2.0  8.0   840  85.2                                     3.5    51   2.9     2.2   A           example 1     Example 42           Preparation                 3.0  7.0   1070 93.5                                     2.7    53   4.3     0.2   B           example 1     Example 43           Preparation                 4.5  5.5   770  81.0                                     3.6    43   2.6     1.4   A           example 1     Example 44           Preparation                 2.0  8.0   960  86.2                                     3.5    62   4.4     1.9   A           example 2     Example 45           Preparation                 3.0  7.0   1120 92.8                                     2.9    56   5.8     0.3   A           example 2     Example 46           Preparation                 4.5  5.5   850  87.0                                     3.4    42   3.7     1.1   A           example 2     __________________________________________________________________________

Comparative Examples 7 to 10

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 and 2 except for changing the formulation amounts of the binder resins (B) and the components (C) so that the weights (unit: g) of the binder resins (B) and the weights (unit: g, solid content) of the components (C) had relations as shown in Table 8. The results are shown in Table 8.

                                      TABLE 8     __________________________________________________________________________                  Binder    Initial                                 Dark       Residual            Charge                  resin                      Component                            charge                                 decay                                     Sensitivity                                            potential    Water            generation                  (B) (C)   V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image            substance                  (g) (g)   (-V) (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Comparative            Preparation                  1.0 9.0   680  78.2                                     12.5   251  48.5    2.9    D'     example 7            example 1     Comparative            Preparation                  7.0 3.0   270  10.5                                     1.7    13   31.4    4.2   F     example 8            example 1     Comparative            Preparation                  1.0 9.0   470  61.0                                     7.6    184  37.2    3.4    C'     example 9            example 2     Comparative            Preparation                  7.0 3.0   360  46.2                                     1.5    3    29.9    3.9   F     example 10            example 2     __________________________________________________________________________

EXAMPLES 47 TO 50

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 to 4 except for using a mixed solvent of 2-ethoxyethanol and ethyl acetate (2-ethoxyethanol:ethyl acetate=6:4 (weight ratio)) in place of 2-ethoxyethanol. The results are shown in Table 9.

                                      TABLE 9     __________________________________________________________________________                         Initial                              Dark        Residual     Charge              charge                              decay                                   Sensitivity                                          potential     Water     generation   Mixed  V.sub.0                              DDR  E.sub.1/2                                          Vr    Precipitability                                                        absorption                                                               Image     substance    solvent                         (-V) (%)  (mJ/m.sup.2)                                          (-V)  (%)     (%)    quality     __________________________________________________________________________     Example 47           Preparation                  2-Ethoxy                         930  85.3 3.12   50    12.1    2.8    B           example 1                  ethanol:     Example 48           Preparation                  ethyl  850  88.3 3.88   36    10.3    2.4    A           example 2                  acetate =     Example 49           Preparation                  6:4    880  87.4 3.66   43    14.4    1.7    A           example 3     Example 50           Preparation   790  90.3 3.24   38    9.8     1.8    B           example 4     __________________________________________________________________________

EXAMPLES 51 TO 58

Electrophotographic photoreceptors were prepared and evaluated according to Examples 1 and 2 except for using 2-ethoxyethanol and tetrahydrofuran (described as "THF" in Table 10) or methyl ethyl ketone (described as "MEK" in Table 10) which was a solvent having an evaporation rate larger than that of 2-ethoxyethanol, and using mixed solvents formulated at weight ratios shown in Table 10. The results are shown in Table 10.

                                      TABLE 10     __________________________________________________________________________                            Initial                                 Dark       Residual     Charge           2-Ethoxy-                            charge                                 decay                                     Sensitivity                                            potential    Water     generation       ethanol:                            V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image     substance   Solvent                      solvent                            (-V) (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Example 51           Preparation                 THF  7:3   840  82.3                                     4.30   68   15.3    1.3   B           example 1     Example 52           Preparation                 THF  3:7   890  90.3                                     3.95   44   8.2     2.1   B           example 1     Example 53           Preparation                 MEK  7:3   780  84.6                                     4.41   81   4.8     0.8   A           example 1     Example 54           Preparation                 MEK  3:7   820  87.5                                     3.53   68   7.6     1.6   A           example 1     Example 55           Preparation                 THF  7:3   780  81.6                                     3.58   59   13.8    1.1   A           example 2     Example 56           Preparation                 THF  3:7   820  85.5                                     4.22   75   11.2    1.5   B           example 2     Example 57           Preparation                 MEK  7:3   910  92.7                                     2.73   64   9.5     0.8   A           example 2     Example 58           Preparation                 MEK  3:7   860  88.8                                     3.26   68   8.5     1.9   A           example 2     __________________________________________________________________________

EXAMPLE 59

An electrophotographic photoreceptor was prepared and evaluated according to Example 1 except for using 1-methoxy-2-propanol in place of 2-ethoxyethanol as the solvent (D) having both a hydroxyl group and an ether group in one molecule. The results are shown in Table 11.

EXAMPLE 60

An electrophotographic photoreceptor was prepared and evaluated according to Example 1 except for using the β type copper phthalocyanine obtained in Preparation example 6. The results are also shown in Table 11.

EXAMPLE 61

An electrophotographic photoreceptor was prepared and evaluated according to Example 1 except for using l type nonmetal phthalocyanine (produced by Toyo Ink Co.). The results are shown in Table 11.

EXAMPLE 62

An electrophotographic photoreceptor was prepared and evaluated according to Example 1 except for using chloroaluminum phthalocyanine (produced by Kodak Co.). The results are shown in Table 11.

EXAMPLES 63 TO 65

Electrophotographic photoreceptors were prepared and evaluated according to Example 1 except for using the titanylphthalocyanine compositions obtained in Preparation examples 5, 3 and 4, respectively. The results are shown in Table 11.

                                      TABLE 11     __________________________________________________________________________                          Initial                               Dark       Residual     Charge          Charge                          charge                               decay                                   Sensitivity                                          potential     Water     generation      transport                          V.sub.0                               DDR E.sub.1/2                                          Vr    Precipitability                                                        absorption                                                               Image     substance       substance                          (-V) (%) (mJ/m.sup.2)                                          (-V)  (%)     (%)    quality     __________________________________________________________________________     Example 59           Preparation                     No. 1                          850  93.3                                   2.98   48    0.2     0.8    A           example 1     Example 60           Preparation                     No. 1                          950  87.4                                   5.96   58    6.2     1.1    A           example 6     Example 61           ι Type non-metal                     No. 1                          780  88.3                                   4.38   39    5.4     1.4    A           phthalocyanine     Example 62           Chloroaluminum                     No. 1                          720  81.2                                   3.97   25    8.8     1.3    A           phthalocyanine     Example 63           Preparation                     No. 1                          940  95.5                                   2.73   37    0.3     0.5    A           example 5     Example 64           Preparation                     No. 1                          850  91.4                                   3.15   63    0.9     0.7    A           example 3     Example 65           Preparation                     No. 1                          910  92.2                                   3.02   44    0.4     0.9    A           example 4     __________________________________________________________________________

EXAMPLES 66 TO 72

Electrophotographic photoreceptors were prepared and evaluated according to Examples 59 to 65 except for using a polyvinyl butyral resin Ethlec BMS (trade name, produced by Sekisui Kagaku Kogyo Co.) (the compound of the formula (I) wherein R is an n-butylene group, R¹ is a methyl group, k is 0.70, m is 0.05 and n is 0.25) in place of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) as the binder resin (B) and formulating 2.22 g of the polyvinyl butyral resin Ethlec BMS (trade name, produced by Sekisui Kagaku Kogyo Co.) and 15.25 g of the melamine resin ML289 (trade name, produced by Hitachi Chemical Co., Ltd.). The results are shown in Table 12.

                                      TABLE 12     __________________________________________________________________________                          Initial                               Dark       Residual     Charge          Charge                          charge                               decay                                   Sensitivity                                          potential     Water     generation      transport                          V.sub.0                               DDR E.sub.1/2                                          Vr    Precipitability                                                        absorption                                                               Image     substance       substance                          (-V) (%) (mJ/m.sup.2)                                          (-V)  (%)     (%)    quality     __________________________________________________________________________     Example 66           Preparation                     No. 1                          920  94.3                                   3.21   48    0.6     1.5    A           example 1     Example 67           Preparation                     No. 1                          960  90.4                                   6.03   58    7.3     1.6    A           example 6     Example 68           ι Type non-metal                     No. 1                          850  85.3                                   4.72   39    5.8     2.2    A           phthalocyanine     Example 69           Chloroaluminum                     No. 1                          730  80.2                                   3.11   25    8.2     1.8    A           phthalocyanine     Example 70           Preparation                     No. 1                          1120 95.6                                   2.65   28    3.6     0.9    A           example 5     Example 71           Preparation                     No. 1                          1090 91.2                                   3.28   38    1.8     1.6    A           example 3     Example 72           Preparation                     No. 1                          860  93.4                                   3.52   43    2.2     1.8    A           example 4     __________________________________________________________________________

EXAMPLES 73 TO 96

Electrophotographic photoreceptor were prepared and evaluated according to Examples 59 to 65 except for using cross-linking agents (Component (C)) shown in Table 13 in place of the malamin resin ML289 (trade name, produced by Hitachi Chemical Co., Ltd.) and formulating 3.95 g of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) and 12.1 g of the crosslinking agents. The results are shown in Table 13. In Table 13, ML245 is a melamine resin ML245 (trade name, produced by Hitachi Chemical Co., Ltd., solid content: 50.0% by weight) and ML365 is a benzoguanamine resin ML365 (trade name, produced by Hitachi Chemical Co., Ltd., solid content: 50.0% by weight). Further, water absorption was evaluated from weight change during drying with silica gel and under moisture conditioning with an NH₄ H₂ PO₄ -saturated aqueous solution, and the results are also shown in Table 13.

                                      TABLE 13     __________________________________________________________________________                                Initial                                    Dark      Residual     Charge         Charge      charge                                    decay                                        Sensitivity                                              potential   Water     generation     transport                         Crosslinking                                V.sub.0                                    DDR E.sub.1/2                                              Vr   Precipitability                                                          absorption                                                                Image     substance      substance                         agent  (-V)                                    (%) (mJ/m.sup.2)                                              (-V) (%)    (%)   quality     __________________________________________________________________________     Example 73           Preparation                    No. 1                         ML245  850 91.3                                        2.98  48   0.6    1.2   A           example 1     Example 74           Preparation                    No. 1                         ML365  920 92.5                                        2.61  48   0.7    1.4   A           example 1     Example 75           Preparation                    No. 1                         ML245  890 87.4                                        5.96  58   6.2    0.8   A           example 6     Example 76           Preparation                    No. 1                         ML365  930 89.6                                        5.66  62   5.6    1.1   A           example 6     Example 77           ι Type non-metal                    No. 1                         ML245  780 88.3                                        4.38  39   5.4    0.5   A           phthalocyanine     Example 78           ι Type non-metal                    No. 1                         ML365  930 90.2                                        4.26  38   3.8    0.9   A           phthalocyanine     Example 79           Chloroaluminum                    No. 1                         ML245  720 81.2                                        3.97  25   8.8    1.3   A           phthalocyanine     Example 80           Chloroaluminum                    No. 1                         ML365  760 82.3                                        3.65  31   7.5    1.7   A           phthalocyanine     Example 81           Preparation                    No. 1                         ML245  840 89.5                                        3.34  57   1.3    1.4   A           example 5     Example 82           Preparation                    No. 1                         ML365  890 90.2                                        3.55  55   1.2    0.8   A           example 5     Example 83           Preparation                    No. 1                         ML245  850 91.4                                        2.71  53   0.9    1.5   A           example 3     Example 84           Preparation                    No. 1                         ML365  900 92.2                                        3.18  49   1.0    1.2   A           example 3     Example 85           Preparation                    No. 1                         ML245  910 92.2                                        3.02  64   1.1    0.7   A           example 4     Example 86           Preparation                    No. 1                         ML365  890 93.4                                        2.76  58   0.4    1.3   A           example 4     __________________________________________________________________________

Comparative Examples 11 to 24

Electrophotographic photoreceptors were prepared and evaluated according to Examples 59 to 65 except for using an acryl resin Almatex WP640 (trade name, produced by Mitsui Toatsu Kagaku Co.) or an acrylic resin Elvacite 2045 (trade name, produced by Du'Pont de Nemours) in place of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) as the binder resin (B). The results are shown in Table 14.

                                      TABLE 14     __________________________________________________________________________                               Initial                                   Dark       Residual            Charge   Charge                          Binder                               charge                                   decay                                       Sensitivity                                              potential   Water            generation                     transport                          resin                               V.sub.0                                   DDR E.sub.1/2                                              Vr   Precipitability                                                          absorption                                                                Image            substance                     substance                          (B)  (-V)                                   (%) (mJ/m.sup.2)                                              (-V) (%)    (%)   quality     __________________________________________________________________________     Comparative            Preparation                     No. 1                          Almatex                               1030                                   98.2                                       8.92   740  19.6   2.1    B'     example 11            example 1     WP640     Comparative            Preparation                     No. 1     1120                                   97.1                                       9.33   850  32.5   2.3    B'     example 12            example 6     Comparative            ι Type non-metal                     No. 1     1122                                   96.2                                       Measurement                                              980  56.2   3.1   F     example 13            phthalocyanine             was                                       impossible     Comparative            Chloroaluminum                     No. 1     1030                                   90.1                                       7.57   400  66.6   2.8    B'     example 14            phthalocyanine     Comparative            Preparation                     No. 1     1220                                   99.3                                       Measurement                                              1160 55.4   2.9   F     example 15            example 5                  was                                       impossible     Comparative            Preparation                     No. 1     1000                                   96.2                                       12.2   760  62.7   3.2   E     example 16            example 3     Comparative            Preparation                     No. 1     950 97.9                                       11.5   530  48.8   2.8    D'     example 17            example 4     Comparative            Preparation                     No. 1                          Elvacite                               560 65.2                                       5.82   320  50.4   2.4    C'     example 18            example 1     2045     Comparative            Preparation                     No. 1     825 55.0                                       6.23   420  61.3   3.2   E     example 19            example 6     Comparative            ι Type non-metal                     No. 1     320 36.8                                       0.23   240  72.5   3.7   F     example 20            phthalocyanine     Comparative            Chloroaluminum                     No. 1     70  11.2                                       Measurement                                              40   50.9   4.3   F     example 21            phthalocyanine             was                                       impossible     Comparative            Preparation                     No. 1     480 60.3                                       4.59   330  61.3   2.6   E     example 22            example 5     Comparative            Preparation                     No. 1     520 65.5                                       5.12   500  58.4   3.5   F     example 23            example 3     Comparative            Preparation                     No. 1     550 58.8                                       6.97   510  65.4   2.9   F     example 24            example 4     __________________________________________________________________________

Comparative Examples 25 to 31

Electrophotographic photoreceptors were prepared and evaluated according to Examples 59 to 65 except for using an epoxy resin Epikote 828 (trade name, produced by Yuka Shell Epoxy Co.) in place of the melamine resin ML289 (trade name, produced by Hitachi Chemical Co., Ltd.) as a cross-linking agent (Component (C)) and formulating 1.0 g of the polyvinyl acetal resin Ethlec KS-5Z (trade name, produced by Sekisui Kagaku Kogyo Co.) and 3.5 g of the-epoxy resin Epikote 828 (trade name, produced by Yuka Shell Epoxy Co.). The results are shown in Table 15. Further, water absorption was evaluated from weight change during drying and under moisture conditioning with an NH₄ H₂ PO4-saturated aqueous solution, and the results are also shown in Table 15.

                                      TABLE 15     __________________________________________________________________________                               Initial                                   Dark       Residual            Charge   Charge                          Cross-                               charge                                   decay                                       Sensitivity                                              potential   Water            generation                     transport                          linking                               V.sub.0                                   DDR E.sub.1/2                                              Vr   Precipitability                                                          absorption                                                                Image            substance                     substance                          agent                               (-V)                                   (%) (mJ/m.sup.2)                                              (-V) (%)    (%)   quality     __________________________________________________________________________     Comparative            Preparation                     No. 1                          Epikote                               510 55.8                                       2.03   20   35.5   5.6    C'     example 25            example 1     828     Comparative            Preparation                     No. 1     530 60.2                                       4.58   50   38.8   5.4    B'     example 26            example 6     Comparative            ι Type non-metal                     No. 1     325 40.3                                       Measurement                                              10   56.8   5.7   F     example 27            phthalocyanine             was                                       impossible     Comparative            Chloroaluminum                     No. 1     50  12.2                                       Measurement                                              0    72.5   5.4   F     example 28            phthalocyanine             was                                       impossible     Comparative            Preparation                     No. 1     435 65.4                                       2.92   30   45.5   5.5   F     example 29            example 5     Comparative            Preparation                     No. 1     380 49.5                                       1.31   20   36.7   5.7   F     example 30            example 3     Comparative            Preparation                     No. 1     470 54.8                                       0.83   10   43.3   5.6    B'     example 31            example 4     __________________________________________________________________________

EXAMPLES 87 TO 96

Electrophotographic photoreceptors were prepared and evaluated according to Examples 59 to 65 except for changing the formulation amounts of the binder resin and the cross-linking agent (Component (C)) so that the weight of the binder resin (described as "BP" in Table 16) and the weight of the crosslinking agent (described as "CA" in Table 16, shown in terms of a weight of a solid component) had relations shown in Table 16. The results are shown in Table 16.

                                      TABLE 16     __________________________________________________________________________                             Initial                                 Dark       Residual     Charge             Charge                             charge                                 decay                                     Sensitivity                                            potential    Water     generation         transport                             V.sub.0                                 DDR E.sub.1/2                                            Vr   Precipitability                                                         absorption                                                               Image     substance      BP:CA                        substance                             (-V)                                 (%) (mJ/m.sup.2)                                            (-V) (%)     (%)   quality     __________________________________________________________________________     Example 87           Preparation                    3.2:6.8                        No. 1                             850 93.3                                     3.18   52   0.8     1.3   A           example 1     Example 88           Preparation                    1.8:8.2                        No. 1                             1020                                 89.8                                     2.70   47   1.7     2.1   A           example 1     Example 89           Preparation                    3.2:6.8                        No. 1                             950 88.4                                     5.96   58   7.1     1.4   A           example 6     Example 90           Preparation                    1.8:8.2                        No. 1                             1010                                 91.2                                     6.03   63   2.3     1.9   A           example 6     Example 91           ι Type non-metal                    3.2:6.8                        No. 1                             740 84.3                                     4.38   51   4.6     1.6   A           phthalocyanine     Example 92           ι Type non-metal                    1.8:8.2                        No. 1                             820 86.2                                     4.56   48   5.8     2.3   A           phthalocyanine     Example 93           Chloroaluminum                    3.2:6.8                        No. 1                             750 80.3                                     3.88   28   8.7     1.8   A           phthalocyanine     Example 94           Chloroaluminum                    1.8:8.2                        No. 1                             720 82.2                                     4.17   23   9.8     1.9   A           phthalocyanine     Example 95           Preparation                    3.2:6.8                        No. 1                             830 87.2                                     3.39   43   1.4     1.4   A           example 5     Example 96           Preparation                    1.8:8.2                        No. 1                             940 84.5                                     3.64   57   1.3     2.2   A           example 5     __________________________________________________________________________

EXAMPLES 97 TO 106

Electrophotographic photoreceptors were prepared and evaluated according to Examples 59 to 65 except for using mixed solvents of 1-methoxy-2-propanol and methyl ethyl ketone (described as "MEK" in Table 17) formulated at weight ratios shown in Table 17 in place of 1-methoxy-2-propanol. The results are shown in Table 17.

                                      TABLE 17     __________________________________________________________________________                                Initial                                    Dark      Residual            Charge   1-Methoxy-                           Charge                                charge                                    decay                                        Sensitivity                                              potential   Water            generation                     2-propanol:                           transport                                V.sub.0                                    DDR E.sub.1/2                                              Vr   Precipitability                                                          absorption                                                                Image            substance                     MEK   substance                                (-V)                                    (%) (mJ/m.sup.2)                                              (-V) (%)    (%)   quality     __________________________________________________________________________     Example 97            Preparation                     70:30 No. 1                                880 92.4                                        2.91  53   1.9    1.5   A            example 1     Example 98            Preparation                     30:70 No. 1                                910 90.2                                        3.15  55   3.3    0.9   A            example 1     Example 99            Preparation                     70:30 No. 1                                950 86.4                                        5.76  48   8.6    1.3   A            example 6     Example 100            Preparation                     30:70 No. 1                                840 85.2                                        5.93  56   12.3   1.4   A            example 6     Example 101            ι Type non-metal                     70:30 No. 1                                820 82.2                                        4.66  63   5.5    0.8   A            phthalocyanine     Example 102            ι Type non-metal                     30:70 No. 1                                830 85.2                                        4.21  59   7.3    1.7   A            phthalocyanine     Example 103            Chloroaluminum                     70:30 No. 1                                700 78.3                                        3.28  28   8.9    1.5   A            phthalocyanine     Example 104            Chloroaluminum                     30:70 No. 1                                710 75.5                                        3.22  26   14.6   1.8   A            phthalocyanine     Example 105            Preparation                     70:30 No. 1                                970 87.2                                        3.29  35   3.4    0.6   A            example 5     Example 106            Preparation                     30:70 No. 1                                1020                                    89.5                                        3.54  54   3.3    1.3   A            example 5     __________________________________________________________________________

EXAMPLES 107 TO 116

Electrophotographic photoreceptors were prepared and evaluated according to Examples 59 to 65 except for using mixed solvents of 1-methoxy-2-propanol and ethyl acetate (described as "AcOEt" in Table 18) formulated at weight ratios shown in Table 18 in place of 1-methoxy-2-propanol. The results are shown in Table 18.

                                      TABLE 18     __________________________________________________________________________                                Initial                                    Dark      Residual            Charge   1-Methoxy-                           Charge                                charge                                    decay                                        Sensitivity                                              potential   Water            generation                     2-propanol:                           transport                                V.sub.0                                    DDR E.sub.1/2                                              Vr   Precipitability                                                          absorption                                                                Image            substance                     AcOEt substance                                (-V)                                    (%) (mJ/m.sup.2)                                              (-V) (%)    (%)   quality     __________________________________________________________________________     Example 107            Preparation                     70:30 No. 1                                920 86.5                                        3.00  52   3.8    1.6   A            example 1     Example 108            Preparation                     30:70 No. 1                                810 88.4                                        3.22  38   4.5    1.2   A            example 1     Example 109            Preparation                     70:30 No. 1                                940 89.4                                        5.86  65   9.5    1.5   A            example 6     Example 110            Preparation                     30:70 No. 1                                1120                                    88.2                                        6.35  97   13.5   1.8   A            example 6     Example 111            ι Type non-metal                     70:30 No. 1                                870 85.4                                        4.27  63   8.4    1.0   A            phthalocyanine     Example 112            ι Type non-metal                     30:70 No. 1                                820 81.0                                        4.48  43   12.2   1.6   A            phthalocyanine     Example 113            Chloroaluminum                     70:30 No. 1                                740 73.9                                        3.28  42   10.3   1.8   A            phthalocyanine     Example 114            Chloroaluminum                     30:70 No. 1                                690 69.8                                        3.22  32   16.8   2.3   A            phthalocyanine     Example 115            Preparation                     70:30 No. 1                                950 85.5                                        3.57  52   4.3    0.8   A            example 5     Example 116            Preparation                     30:70 No. 1                                970 86.6                                        3.78  75   5.6    1.5   A            example 5     __________________________________________________________________________

Comparative Examples 32 to 41

Electrophotographic photoreceptors were prepared and evaluated according to Examples 59 to 65 except for using methyl ethyl ketone (described as "MEK" in Table 19) or ethyl acetate (described as "AcOEt" in Table 19) in place of 1-methoxy-2-propanol. The results are shown in Table 19.

                                      TABLE 19     __________________________________________________________________________                               Initial                                   Dark       Residual            Charge        Charge                               charge                                   decay                                       Sensitivity                                              potential   Water            generation                     Kind of                          transport                               V.sub.0                                   DDR E.sub.1/2                                              Vr   Precipitability                                                          absorption                                                                Image            substance                     solvent                          substance                               (-V)                                   (%) (mJ/m.sup.2)                                              (-V) (%)    (%)   quality     __________________________________________________________________________     Comparative            Preparation                     MEK  No. 1                               860 62.4                                       6.27   92   73.4   1.9    B'     example 32            example 1     Comparative            Preparation                     AcOEt                          No. 1                               720 57.7                                       14.27  55   78.2   2.5    C'     example 33            example 1     Comparative            Preparation                     MEK  No. 1                               950 73.4                                       6.88   103  68.6   1.7    B'     example 34            example 6     Comparative            Preparation                     AcOEt                          No. 1                               420 31.3                                       Measurement                                              89   75.6   2.0   F     example 35            example 6                  was                                       impossible     Comparative            ι Type non-metal                     MEK  No. 1                               700 68.8                                       7.31   230  58.5   1.6    C'     example 36            phthalocyanine     Comparative            ι Type non-metal                     AcOEt                          No. 1                               1320                                   96.8                                       12.85  450  69.3   1.8    B'     example 37            phthalocyanine     Comparative            Chloroaluminum                     MEK  No. 1                               620 55.2                                       1.05   18   72.3   1.9   F     example 38            phthalocyanine     Comparative            Chloroaluminum                     AcOEt                          No. 1                               430 37.2                                       Measurement                                              6    74.6   2.5   F     example 39            phthalocyanine             was                                       impossible     Comparative            Preparation                     MEK  No. 1                               720 75.8                                       9.66   472  68.2   1.7   E     example 40            example 5     Comparative            Preparation                     AcOEt                          No. 1                               554 45.3                                       Measurement                                              103  75.5   2.1   F     example 41            example 5                  was                                       impossible     __________________________________________________________________________

The coating solution for forming a charge generation layer of the present invention has excellent dispersion stability (e.g. property of being hardly precipitated), coating property and environmental sanitation, and the electrophotographic photoreceptor using this coating solution has excellent electrophotographic characteristics such as charging characteristics, dark decay and sensitivity so that it can be applied suitably to an electrophotographic process in which density and quality higher than those of the prior art are demanded. 

We claim:
 1. A coating solution for forming a charge generation layer, which comprises:(A) a phthalocyanine composition containing titanylphthalocyanine, (B) a binder resin represented by the formula: ##STR5## wherein R represents an alkylene group, R¹ represents an alkyl group; and m, n and k each represent a ratio of recurring unit numbers and are numerals satisfying the relations of k+m+n=1, n>m>0 and 0.3≧k≧0, (C) at least one of a melamine resin and a benzoguanamine resin in an amount of 1- to 5-fold in terms of the weight ratio based on the amount of the binder resin, and (D) a solvent having both a hydroxyl group and an ether group in one molecule.
 2. The solution according to claim 1, wherein the phthalocyanine composition comprises titanylphthalocyanine and a halogenated metal phthalocyanine in which a central metal is trivalent.
 3. The solution according to claim 2, wherein the phthalocyanine composition comprises 20 to 95% by weight of titanylphthalocyanine and the reminder being a halogenated metal phthalocyanine in which a central metal is trivalent.
 4. The solution according to claim 3, wherein the phthalocyanine composition comprises 75 to 90% by weight of titanylphthalocyanine and the reminder being a halogenated metal phthalocyanine in which a central metal is trivalent.
 5. The solution according to claim 2, wherein the phthalocyanine composition is obtained by making amorphous a phthalocyanine mixture of titanylphthalocyanine and a halogenated metal phthalocyanine in which a central metal is trivalent and then treating the resulting amorphous mixture with an organic solvent.
 6. The solution according to claim 2, wherein the trivalent metal is indium.
 7. The solution according to claim 1, wherein the phthalocyanine composition (A) has main diffraction peaks at 7.5°, 22.5°, 24.3°, 25.3° and 28.6° of Bragg angles (2θ±0.2°) in an X-ray diffraction spectrum with Cu Kα.
 8. The solution according to claim 1, wherein R in the formula (I) is an alkylene group having 1 to 4 carbon atoms and R¹ is a methyl group.
 9. The solution according to claim 1, wherein the binder resin has a number average molecular weight of 300 to
 3000. 10. The solution according to claim 1, wherein the melamine resin or benzoguanamine resin (C) is a resin in which 50% or more of amino groups bonded to a triazine ring is converted into methylol groups and 50% or more of the methylol groups is modified by an alcohol.
 11. The solution according to claim 1, wherein the melamine resin or benzoguanamine resin (C) is used in an amount of 1.3 to 3-fold in terms of weight based on the amount of the binder resin (B).
 12. The solution according to claim 1, wherein the melamine resin or benzoguanamine resin (C) are used in total in an amount of 1.5 to 2.5-fold in terms of weight based on the amount of the binder resin (B).
 13. The solution according to claim 1, wherein the binder resin (B) and the melamine resin or benzoguanamine resin (C) are used in total in an amount of 5 to 500% by weight based on the amount of the phthalocyanine composition (A).
 14. A coating solution for forming a charge generation layer, which comprises:(A) a phthalocyanine composition, (B) a binder resin represented by the formula: ##STR6## wherein R represents an alkylene group, R¹ represents an alkyl group; and m, n and k each represent a ratio of recurring unit numbers and are numerals satisfying the relations of k+m+n=1, n>m>0 and 0.3≧k≧0, (C) at least one of melamine resin and a benzoguanamine resin in an amount of 1- to 5-fold in terms of the weight ratio based on the amount of the binder resin, and (D) a solvent selected from the group consisting of 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol and 1-propoxy-2-propanol.
 15. The solution according to claim 14, wherein the solvent (D) is 1-methoxy-2-propanol.
 16. The solution according to claim 1, wherein the solution further contains a solvent (E) other than the solvent (D).
 17. The solution according to claim 16, wherein the solvent (E) has a higher evaporation rate than that of the solvent (D).
 18. The solution according to claim 17, wherein both of the solvent (D) and the solvent (E) do not contain a halogen atom.
 19. The solution according to claim 16, wherein the solvent (D) is contained in an amount of 20 to 100% by weight based on the total amount of the solvents (D) and (E).
 20. An electrophotographic photoreceptor which comprises the coating solution for forming a charge generation layer according to claim
 1. 21. The solution according to claim 1, wherein the solvent (D) is selected from the group consisting of 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol and 1-propoxy-2-propanol.
 22. The solution according to claim 21, wherein the solvent (D) is 1-methoxy-2-propanol. 